Thiosulfenyl chlorides and bromides and polymers made therefrom



Patented July 27, 1954 UNITED STATES THIOSULFENYL CHLORIDES AND BROMIDES AND POLYMERS MADE THEREFROM TENT OFFICE No Drawing. Application December 22, 1950, Serial No. 202,428

16 Claims. (01. zen-2.3) l 2 This invention relates to processes for the terials (L. A. Wood, Synthetic Rubbersll 'Rechlorination and bromination of certain organic view of Their Compositions, Properties and tetrasulfides containing the linkage Usescircular 427 of U. S. Dept. of Commerce,

Nat. Bureau of Standards (1946)). The chlorinolysis and brominolysi of the polymeric orand to certain novel products produced by Sa ganic tetrasulfides lead to the formation of novel processes. In a more specific aspect, this invenbis-thiosulfenyl chlorides and bromides. tion relates to a pr ce the preparation of Typical polymeric rubber-like organic tetrabis-thiosulfenyl chlorides and bromides and the sulfides cgntaining as h as one-half of th i novel compounds thereby obtained. sulfur content in the form of side-chain sulfur One obJect of the present invention is to p contain the following characteristic groupings:

vide a process for the chlorinolysis and brominolysis of polymeric organic tetrasuliides having the (CH2CH2 S4 -CH2S4CH2- grouping. Another object is (CHzCH2--O-- CH2CI-Iz- S4)n to provide a novel process for the preparation of '15 CH CH bis-thiosulfenyl chlorides and bromides. An ad- 2 2 CH2 4 ditional object is to provide the art with novel f bis-thiosulfenyl chlorides and bromides. Still (CHCHrS4)- anotherfobjelct of the rl lvegtilon istodprovirge a process or 1550 ving 10 c or er.uren ype go polysulfide polymers in organic solvents and to '(CH2CH=CH CH2 S4 provide processes for regenerating synthetic rubn being an integer greater than 1. ber-like mater als from these solutions. Still another ob ect 1s to provide a process for recovering or reclaiming synthetic tetrasulfide rubbers OH from scrap or waste fabricated materials contain --(CH2CH2-OCH2CH2O-CH2CH2S4-) n ing the same. A further object of the presentin- These materials usually have very high melecmaur vention is to provide a process ror the preparation Weights and are charactgrized by their substantial of novel synthetic IllbDGl-llkG latices. insglubihty in most organic Solvents.

Bnefly I h ffmnd that E f a The polymeric rubber-like organic tetrasultetraSu 1fides m which one or P P h Sulfm fides having the structures specifically illustrated aitgms the tetrasulfid? grow-9mg 15 attached as above contain as the repeating unit a plurality of side-chain sulfur (coordinate sulfur) can be congroups in which at least one of the verted by ChIOIII IOIYSIS or brominclysis to the sulfur atoms is mc id a "form a in il corresponding thiosulfenyl chloride or bromide. Z represents a bivalent Organic radical directly The point of SCl-SSIOII by chlorine or bromine in connected to the group through a carbon the polymeric organic tetrasulfides of the above atom' having atleast one hydrogfin'atom attached description is definitely marked; the scission thereto chlorinolysis or brominolysis of p013 process appears to betselteiftive and un q f mers containing said repeating unit yields proding almost entirely vo e production of thlo- 40 ucts having the formula sulfenyl chlorides and biomides, rather than to wherein Z retains the definition given above and the formation of random chlorinolysis and X is chlorine or bromirle' brominolysls products, as would be e pt The By Way of illustration, the chlorinolysis and expected chlormolysi and brominolysis products brominolysis products obtainable from pmymer's from polymeric organic tetrasulfides containing ha'Vin esesntiau h .ucture the grouping CI-I2S4-CH2 would be comg y pounds containing the CSX grouping and S2X2, (CH2CH2S4)-n wherein X is chlorine or bromine, by analogy with caustic scission of these com ounds, hich commonly known as Thlokol have tr-1e formula W X- s s-oH2oH2 s s-X and from (CH2CH2-O'CH2CH2'S4-) nhas been found to remove the relatively labile side-chain sulfur atoms (S. M. Martin and J. C. Patrick, Ind. Eng. Chem. 28, 1147 (October 1936) (Thiokol B) have the formula.

A preferred class of tetrasulfide compounds I comprises the Thiokol or Perduren-type polymeric poly-tetrasulfide synthetic rubber-like mawherein Xis chlorine or bromine.

The general method of operation which I cmploy is to dissolve or disperse the polymeric organic tetrasulfide in a solvent for the chlorinolysis and brominolysis reaction products, for example a halogenated hydrocarbon solvent such as chloroform, carbon tetrachloride, 1,2-dichloroethane, perfluoroheptane; n-octane, benzene, furfural, dibutyl phthalate, tricresyl phosphate, ethyl acetate or other inert solvent. The chlorine or bromine is then introduced into the solution or mixture while effecting intimate contacting between the reactants, usually by the use of a mechanical stirring device. The chlorinolysis and brominolysis reactions are highly exothermic; consequently, heat must be removed from the reaction zone during the course of the reaction to maintain suitable reaction temperatures and to prevent runaway reactions which lead to the formation of tars and other nondescript products. Conventional cooling methods may be employed to maintain the desired reaction temperatures. A particularly desirable cooling method involves circulation of the reaction solvent (as a liquid or vapor) to a cooling zone, thence back to the reaction zone.

Suitable reaction temperatures are between about 50 C. and about 25 (3., preferably about C. to about C. Reaction can readily be effected at or about atmospheric pressure, but elevated pressures, for example to 200 p. s. i. g., can be employed, provided that the reaction temperature can be adequately controlled by maintaining a relatively low instantaneous concentration of chlorine or bromine in the reaction zone, by maintaining a high rate of circulation of the reaction solvent between cooling and reaction zones, etc.

The reaction between chlorine or bromine and the polymeric organic tetrasulfide appears to be rapid and to be limited, primarily, only by the rate of introduction of the halogen into intimate contact with the organic tetrasulfide. When solid tetrasulfides are employed, the particle size and shape are factors in the rate of reaction. Small particles having a large surface area per unit weight tend to react more rapidly than large particles having a relatively low surface area per unit weight. Suitable reaction periods, in general, vary between about 60 and about 180 minutes although it should be understood that the choice of reaction period will necessarily depend upon the prior selection of other rate-determining variables and is, in general, not critical.

Upon completion of the reaction, a solution of the organic thiosulfenyl chloride in the reaction solvent is obtained. The reaction solvent can be separated from the reaction product by low pressure distillation if desired or, preferably, the solution or a concentrate thereof is employed for various end uses, for example in further reactions to produce desired derivatives.

The present chlorinolysis and brominolysis processes can be employed for recovering and reconverting polysulfide rubbers to forms useful in industrial processing. The process comprises reaction of the contaminated or fabricated material with chlorine at about to about +25 C. in the presence of a solvent, e. g., a halogenated hydrocarbon solvent such as carbon tetrachloride, followed by dispersion of the rich solution in water, preferably, in water containing a reducing agent such as $02, NaSH, NazSzOs, NazSz or the like. The resultant latex can be steamed to remove solvent, or coagulated and desolvented by conventional methods. The resultantprod- 4 not is a latex or rubber useful for the purposes for which the new synthetic rubber is generally used.

The present process permits recovery of Thiokol from fabricated material which has been damaged, such as oil resistant hose, etc., or from fabricated material containing fillers or fibrous solids, an permits separation of these undesirable foreign materials. It also permits reconversion of block polysulfide rubbers to latices and the addition of additives, pigments, etc. to the latex which cannot be blended into the block form.

In order more fully to illustrate the novel processes of the present invention, the following spe- Cific examples are submitted in an illustrative, and not limitative, capacity;

Example 1 Commercial ethylene polysulfide rubber (291 g.), known as Thiokol A and having essentially the structure -(CH2CH2-S4- n, was placed in a weighed flask and 300 cc. of carbon tetrachloride were added to just cover the rubber, which was present as slicings about 0.4 x 3 x 4 cm. in dimension. The sulfur analysis of the Thiokol A was 79.8% and it contained 1.1% of residual chlorine. A stirrer was lowered into the reactor so that it just touched the surface of the solvent. The reactor was immersed in cold water, and chlorine was passed in slowly. The stirrer was run so that a spray of solvent covered the walls of the flask, from which chilled solvent flowed back to the liquid contents in the reactor. After 2.25 hours, 148 g. of chlorine were absorbed. The solid rubber slowly disappeared and a yellow solution was produced. The temperature fell from an initial value of 17 C. to 8 0.; good cooling was necessary to effect this result, as the re-. action is exothermic. The chlorine flow was discontinued and the mixture was stirred for an additional 0.5 hour, during which time a few lumps of unreacted rubber disappeared. The product was vacuum topped at pressures between 5-35 mm. of mercury and yielded 412 g. of a viscous olive green oil which was found on analysis to contain 53.2% S and 29.2% chlorine, by weight. The analysis checks quite closely with the theoretical values for C2H4S4C12, (l,2-bis(chlorothiosulfenyl)ethane), which are 56.3% S and 31.2% chlorine. The product showed n 1.7035 and Example 2 Thiokol A (125.5 g.) was placed in a flask with 150 cc. of chloroform. Chlorine (58.5 g.) was introduced slowly, the flask being immersed in an ice bath, and the flask contents being held at lG-15 C. All the chlorine was in after 1.3 hours. Some Thiokol was still undissolved and the mixe ture was stirred at 15-16 C. until all'solid was gone (so minutes). A slow stream of methan'e thiol gas was then introduced into the flask, with stirring, until an excess had been added. The products were removed after four hours and a portion charged to a distillation assembly. All material boiling below 60 at 0.3 mm. of mercury was topped off and discarded, at which point dis; tillation ceased. The overhead was primarily chloroform, but some high boiling sulfur compounds (about 30 cc.) were eliminated, possibly of the disulfide type, RSSRSSR. The distillation residue of '75 g. of viscous greenish oil was found upon analysis to contain 76.7% S and 0.45% chlorine, by weight. The compound CH3S3C2H4S3CH3 contains 76.4% S and no chlorine. It is therefore evident that the reactions which occurred were as follows:

Example 3 Thiokol-ST, which has essentially the structure:

was stirred with 150 cc. of chloroform and chlorinated with 24.2 g. of chlorine at 13-22 C. over a period of 30 minutes. The mixture was agitated for a short time following the chlorine addition until all residual solid had dissolved. An excess of gaseous isobutene was then introduced into the liquid reaction mixture. The product was vacuum topped to a pot temperature of 135 C. at 3 of mercury Some I-ICl was evolved. The residual oil (90 g.) was found upon analysis to contain 29.8% S and 13% chlorine by weight. The theoretical values for (C4He) 2 (021-140) 2-CH2-S4C12 are 31% S and 17.2% chlorine. While the analytical data indicate some decomposition of the product incidental to distillation, they also indicate that the following reactions occurred:

Emample 4 Thiokol A luinps (48 g.) were stirred with 191 g. of chloroform in a flask immersed in an ice bath. Bromine (49 g.) was introduced into the flask over a period of 35 minutes while the internal temperature therein was maintained at -17 C. The mixture was agitated and allowed to react for 36 minutes following bromine addition, at which time all the synthetic rubber had dissolved. The flask was then maintained at 10-45 C. and an excess of gaseous isobutene was bubbled into the liquid reaction mixture. The reaction products were distilled and all material boiling below 61 C. at 0.5 mm. of mercury was removed. A distillate (14 cc.) with a boiling point above chloroform was recovered. Considerable HBr was evolved in the vacuum distillation process. The distillate analyzed 29.4% S and 31.8% bromine and is therefore an ethane bis-thiosulfenyl bromide-isobute-ne adduct (30% S, 32.4% Br). The brominated adduct with isobutene is less stable than the chlorinated adduct.

Example 5 Thiokol A (73.5 g.) was stirred with 200 cc. of chloroform and chlorinated with 33.5 g. of chlorine at 942 C. Butadiene was passed slowly into the resultant solution until 24.5 g. were absorbed. The mixture was allowed to react at 12-19" C. for a total time of 2.3 hours, including 0.66 hour after all the butadiene had been introduced. Then a large excess of butadiene was added to react with and remove any unreacted halide. About 15 g. of a soft chloroformand oil-insoluble, tacky resin separated out during the reaction with butadiene. The chloroform solution was separated and then evaporated and vacuum topped under the pressure of 1 mm. of mercury at 40 C. to produce, as a residue, a very tacky, soft resin which was not miscible with the chloroform-insoluble resin. The volume of chloroform-soluble resin was 50 cc. and it was found upon analysis to contain 41.8% S and 27.3% chlorine, by weight. The theoretical values for a mono-butadiene adduct of 1,2-bis(chlorothiosulfenyDethane are 45.5% S and 25.4% C1. The chloroform-insoluble resin was reacted with hot water to produce a yellow, tacky resin which appears to be a hydrolyzate. The chloroforminsoluble resin is quite insoluble in oils and water and can be used as a softener or plasticizer for sulfur, imparting toughness and elasticity to the sulfur when employed in amounts of 18-29% by weight.

Example 6 Large pieces of Thiokol A (213 g.) were placed in 109 cc. of carbon tetrachloride and slowly chlorinated over a period of 3 hours at 10-22 C. All the Thiolzol dissolved after 101 g, of chlorine had been introduced. The carbon tetrachloride solvent was removed by distillation at 19-35 mm. of mercury pressure, keeping the pot temperature between 2 and 8 C. The reaction product was 363 g. of an olive green oil, 1,2-bis(ohloro thiosulfenyl) ethane. The reaction product was stirred into water and after a few minutes yielded a sticky rubber. If the water contains a reducing agent, the sulfenyl groups in the reaction product are converted to polysulfides and the original Thiokol rubber is regenerated. If desired, a dispersing agent, such as magnesium hydroxide, can be used to form a latex from the treated rubber.

In the above examples I have, among other things, described the reaction of isobutylene and butadiene, respectively, with l,2-bis(ch orothiosulfenyhethane. It will be apparent that the reactions of organic bis-thiosulfenyl chlorides and bromides can be conducted with other monoand polyole'finic materials, for exampl styrene or divinylbenzene. Moreover, the thiosulfenyl halide products produced by the present inven tion can be reacted with monoor poly-mercaptides. Numerous other derivatives will, no doubt, suggest themselves to those skilled in the art.

Having thus described my invention, what I claim is:

1. A process for the preparation of a bis-thicsulfenyl halide, which process comprises contacting a halogen selected from the class consisting of chlorine and bromine in quantity sui'licient to eifect substantial production of a bis-thiosulfenyl halide under anhydrous conditions with a polymeric organic tetrasulfide having as the repeating unit -ZCH2S4- groups in which at least one of the sulfur atoms is in coordinate form in the molecule and Z is a bivalent organic radical selected from the group consisting of aliphatic hydrocarbons, oxyaliphatic hydrocarbons, hydroxyaliphatic hydrocarbons, and thioaliphatic hydrocarbons, Z is directly attached to the CH2 group through a carbon atom having at least one hydrogen atom attached thereto,

and effecting said contacting at a temperature between about 50 C. and about 25 C. in the presence of an inert solvent to produce a compound having the formula XSS-Z--CH2-SSX, wherein Z is said bivalent organic radical and X is selected from the class consisting of chlorine and bromine.

2. The process of claim 1 wherein said inert solvent is a halogenated hydrocarbon.

3. The process of claim 1 wherein Z is a CI-I2 radical, said halogen is chlorine, and said inert solvent is a low boiling halogenated hydrocarbon.

4. The process of claim 1 wherein Z is a CH2- radical, said halogen is a bromine, and said inert solvent is a low boiling halogenated hydrocarbon.

5. The process of claim 1 which comprises the additional step of treating the reaction products, comprising a compound having the formula XSS-Z-CH2-S\SX, wherein Z is the bivalent organic radical defined in claim 1, with water to produce a synthetic rubber.

6. A process for the preparation of a bis-thiosulfenyl chloride, which process comprises contacting chlorine in quantity sufficient to effect substantial production of a bis-thiosulfenyl chloride under anhydrous conditions with a polymeric organic tetrasulilde having as the repeating unit 'ZCH2-s-i groups in wlnch at least one of the sulfur atoms is in coordinate form in the molecule and Z is a bivalent aliphatic hydrocarbon radical which is directly attached to the ---CH2 group through a carbon atom having at least one hydrogen atom attached thereto, and effecting said contacting at a temperature between about 5'? C. and about 25 C. in the presence of an inert solvent to produce a compound having the formula ClSSZ-CH2-SSC1, wherein Z is said bivalent aliphatic hydrocarbon radical.

'7. A process for the preparation of a bis-thicsulfenyl chloride, which process comprises contacting chlorine in quantity sufficient to effect substantial production of a bis-thiosulfenyl chlo ride under anhydrous conditions with a polymeric organic tetra-sulfide having as the repeating unit ZCH2S4- groups in which at least one of the sulfur atoms is in coordinate form in the molecule and Z is a bivalent oxyaliphatic hydrocarbon radical which is directly attached to the CH2- group through a carbon atom having at least one hydrogen atom attached thereto, and effecting said contacting at a temperature between about 56 C. and about 25 C. in the presence of an inert solvent to produce a compound having the formula C1SSZ--CH2-SSC1 wherein Z is said bivalent oxyaliphatic hydrocarbon radical.

8. A process for the preparation of a bis-thiosulfenyl chloride, which process comprises contacting chlorine in quantity suflicient to effect substantial production of a bis-thiosulfenyl chloride under anhydrous conditions with a polymeric organic tetrasulfide having as the repeating unit -ZCH2-S4 groups in which at least one of the sulfur'atoms is in coordinate form in the molecule and Z is a bivalent thioaliphatic hydrocarbon radical which is directly attached to the -CH2- group through a carbon atom having at least one hydrogen atom attached thereto, and effecting said contacting at a temperature between about -50 C. and about 25 C. in the presence of an inert solvent to produce a compound having the formula ClSS-ZCH2--SSC1, wherein Z is said bivalent thioaliphatic hydrocarbon radical.

9. New compounds having the general formula XSSZ--CH2SSX, in which formula Z represents a bivalent organic radical selected from the group consisting of aliphatic hydrocarbons, oxyaliphatic hydrocarbons, hydroxyaliphatic hydrocarbons, and thioaliphatic hydrocarbons, Z is directly attached to the CH2 group in said formula by a carbon atom having at least one hydrogen atom attached thereto, and X is selected from the class consisting of chlorine and I bromine.

it. As new compounds, 1,2-bis(halogen thiosu1fenyl) ethanes having the formula wherein X is selected from the class consisting of chlorine and bromine.

11. As a new compound, l,2-bis(chlorothiosulfenyhethane, having the formula 12. As a new compound, 1,2-bis(bromothiosuIfenyDetnane, having the formula Br-SSCHzCHz-SSBr 13. A new compound having the formula 14. New compounds having the general formula ClSS-Z-CHz-SSC1, in which formula Z represents a bivalent aliphatic hydrocarbon radical and Z is directly attached to the CH2- group in said formula by a carbon atom having at least one hydrogen atom attached thereto.

15. New compounds having the general formula ClSS -Z-CH2-SSCL in which formula Z represents a bivalent oxyaliphatic hydrocarbon radical and Z is directly attached to the -CH2-- group in said formula by a carbon atom having at least one hydrogen atom attached thereto.

16. New compounds having the general formula o1ss-z -cri2-ssc1, in which formula Z represents a bivalent thioaliphatic hydrocarbon radical and Z is directly attached to the -CH2-- group in said formula by a carbon atom having at least one hydrogen atom attached thereto.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,466,963 Patrick Apr. 12, 1949 FOREIGN PATENTS Number Country Date 412,349 Great Britain June 28, 1934 

1. A PROCESS FOR THE PREPARATION OF A BIS-THIOSULFENYL HALIDE, WHICH PROCESS COMPRISES CONTACTING A HALOGEN SELECTED FROM THE CLASS CONSISTING OF CHLORINE AND BROMINE IN QUANTITY SUFFICIENT TO EFFECT SUBSTANTIAL PRODUCTION OF A BIS-THIOSULFENYL HALIDE UNDER ANHYDROUS CONDITIONS WITH A POLYMERIC ORGANIC TETRASULFIDE HAVING AS THE REPEATING UNIT -Z-CH2-S4- GROUPS IN WHICH AT LEAST ONE OF THE SULFUR ATOMS IS IN COORDINATE FORM IN THE MOLECULE AND Z IS A BIVALENT ORGANIC RADICAL SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC HYDROCARBONS, OXYALIPHATIC HYDROCARBONS, HYDROXYALIPHATIC HYDROCARBONS, AND THIOALIPHATIC HYDROCARBONS, Z IS DIRECTLY ATTACHED TO THE -CH2- GROUP THROUGH A CARBON ATOM HAVING AT LEAST ONE HYDROGEN ATOM ATTACHED THERETO, AND EFFECTING SAID CONTACTING AT A TEMPERATURE BETWEEN ABOUT -50* C. AND BAOUT 25* C. IN THE PRESENCE OF AN INERT SOLVENT TO PRODUCE A COMPOUND HAVING THE FORMULA XSS-Z-CH2-SSX, WHEREIN Z IS SAID BIVALENT ORGANIC RADICAL AND X IS SELECTED FROM THE CLASS CONSISTING OF CHLORINE AND BROMINE. 